KR100492216B1 - Process for The Preparation of SiOH-Functional Carbosilane Dendrimers - Google Patents
Process for The Preparation of SiOH-Functional Carbosilane Dendrimers Download PDFInfo
- Publication number
- KR100492216B1 KR100492216B1 KR10-1998-0009454A KR19980009454A KR100492216B1 KR 100492216 B1 KR100492216 B1 KR 100492216B1 KR 19980009454 A KR19980009454 A KR 19980009454A KR 100492216 B1 KR100492216 B1 KR 100492216B1
- Authority
- KR
- South Korea
- Prior art keywords
- base
- formula
- sir
- organic solvent
- tbme
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
Abstract
본 발명은 SiOH-관능성 카르보실란 덴드리머의 제조 방법을 제공한다.The present invention provides a process for preparing SiOH-functional carbosilane dendrimers.
Description
본 발명은 SiOH-관능성 카르보실란 덴드리머 (dendrimer)의 제조 방법에 관한 것이다.The present invention relates to a process for the preparation of SiOH-functional carbosilane dendrimers.
덴드리머는 고도로 정렬된, 일반적으로는 3차원 구조 및 저중합체 (올리고머) 또는 고중합체 (폴리머)의 분자량 범위 내의 분자량을 갖는 강하게 분지된 분자이다.Dendrimers are strongly branched molecules having a highly ordered, generally three-dimensional structure and molecular weight within the molecular weight range of the oligomer (oligomer) or the high polymer (polymer).
그러나, 통상의 중합체가 항상 특정 분포의 분자량을 보여주는 것에 반하여, 덴드리머는 정확하게 균일한 분자량을 갖도록 조절할 수 있다는 장점을 가지고 있다. 또한, 규정된 수의 반응성 말단기를 갖는 어떤 관능성 덴드리머라도 제조할 수 있다.However, while conventional polymers always show a specific distribution of molecular weight, dendrimers have the advantage that they can be adjusted to have a precisely uniform molecular weight. In addition, any functional dendrimer having a defined number of reactive end groups can be prepared.
동시 계류 중인 미국 특허 출원 제08/785463호에 대응하는 미국 특허 제5 677 410호 및 독일 특허 공개 제19 603 241호는 SiOH-관능성 카르보실란 덴드리머를 기재하고 있다. 이들은, 예를 들면 유기-무기 혼성 물질 및 코팅재 제조용 (예를 들면, 미국 특허 제5 677 410호를 참조), 촉매적 활성 금속 화합물의 결합용 또는 축합-가교성 유기 폴리실록산 조성물 중의 가교제로서 사용된다.US Patent No. 5 677 410 and German Patent Publication No. 19 603 241, corresponding to co-pending US patent application 08/785463, describe SiOH-functional carbosilane dendrimers. They are used, for example, for the preparation of organic-inorganic hybrid materials and coatings (see, eg, US Pat. No. 5,677,410), for the bonding of catalytically active metal compounds or as crosslinking agents in condensation-crosslinkable organic polysiloxane compositions. .
미국 특허 제5 677 410호 및 독일 특허 공개 제19 603 241호에 따르면, SiOH-관능성 카르보실란 덴드리머는 비극성 용매중에서 대응하는 Si-할로겐-관능성 카르보실란 덴드리머와 물을 염기 존재 하에서 반응시킴으로써 제조한다. 트리 유기 아민, 바람직하게는 트리알킬아민을 염기로서 사용하며, 비극성 용매로서 지방족 에테르를 사용한다.According to US Pat. No. 5 677 410 and German Patent Publication No. 19 603 241, SiOH-functional carbosilane dendrimers are prepared by reacting water with a corresponding Si-halogen-functional carbosilane dendrimer in the presence of a base in a nonpolar solvent. do. Triorganic amines, preferably trialkylamines, are used as bases and aliphatic ethers as nonpolar solvents.
그러나, 상기 반응의 단점은 큰 부피의 고체로서 침강되는 부산물 트리알킬아민 염산염을 지루한 작업을 통해 여과 제거시켜야 한다는 것이다. 반응 동안, 농도 구배 및 온도 구배의 결과로서 부반응이 올리고머 형성을 일으키는 쪽으로 일어나기 때문에, 반응 혼합물의 균일한 혼합 수행을 지연시키거나 방해한다.However, a disadvantage of the reaction is that the byproduct trialkylamine hydrochloride, which precipitates as a large volume of solid, must be filtered off through a tedious operation. During the reaction, because side reactions occur towards oligomer formation as a result of concentration gradients and temperature gradients, the uniform mixing of the reaction mixture is delayed or hindered.
따라서, 언급된 단점인 공정 단계의 곤란함 및 매우 낮은 공간-시간 수득량 때문에 미국 특허 제5 677 410호 및 독일 특허 공개 제196 03 241호에 기재된 방법은 SiOH-관능성 카르보실란 덴드리머의 공업적 제조에 상당히 바람직하게 못한 것으로 보여진다.Therefore, the process described in US Pat. No. 5,677,410 and German Patent Publication No. 196 03 241, due to the disadvantages of the process steps and the very low space-time yield, is an industrial method of It appears to be quite undesirable for the manufacture.
따라서, 선행 기술의 공지된 단점이 없는 SiOH-관능성 카르보실란 덴드리머의 제조 방법을 제공하려는 간절한 요구가 있었다.Thus, there is an urgent need to provide a process for preparing SiOH-functional carbosilane dendrimers without the known disadvantages of the prior art.
이제 상기 언급된 단점들이 생성물 및 부산물의 상이한 용해도 특성을 이용함으로써 해결될 수 있음이 밝혀지게 되었다.It has now been found that the above mentioned disadvantages can be solved by using different solubility characteristics of the product and the by-product.
따라서, 본 발명은 하기 화학식 2의 카르보실란 덴드리머와 물을 염기 또는 염기 혼합물 및 유기 용매 하에서 반응시키며, 유기 용매 및 물을 0.5 내지 1.4 중량%, 바람직하게는 0.9 내지 1.1 중량% 비율로 첨가함으로써 하기 화학식 1의 카르보실란 덴드리머를 제조하는 방법을 제공한다.Accordingly, the present invention is to react the carbosilane dendrimer of the formula (2) and water under a base or base mixture and an organic solvent, by adding an organic solvent and water in a proportion of 0.5 to 1.4% by weight, preferably 0.9 to 1.1% by weight Provided is a method of preparing a carbosilane dendrimer of Formula 1.
[화학식 1][Formula 1]
[상기 식 중에서, [In the above formula,
n은 2 내지 6, 바람직하게는 n은 2이고, R은 C1-C18-알킬 및(또는) C6-C20-아릴 (여기서, n값 및 R기는 분자 내에서 같거나 다를 수 있음)이고,n is 2 to 6, preferably n is 2, and R is C 1 -C 18 -alkyl and / or C 6 -C 20 -aryl, wherein the n value and the R group can be the same or different in the molecule )ego,
추가의 기호 및 표시는 Additional symbols and signs are
A) K는 [R4-iSi] (여기서, i는 3 내지 4, 바람직하게는 4임)이거나, 또는A) K is [R 4-i Si], where i is 3 to 4, preferably 4; or
B) K는B) K is
(여기서, i는 m과 동일하며, 3 내지 6, 바람직하게는 i는 m과 동일하며 4임)이고,Where i is equal to m and 3 to 6, preferably i is equal to m and is 4),
a) X는 (OH)이고 a는 1이거나, 또는a) X is (OH) and a is 1, or
b) X는 [(CH2)nSi(OH)R2]이고 a는 1 내지 3, 바람직하게는 a는 3이거나, 또는b) X is [(CH 2 ) n Si (OH) R 2 ] and a is 1 to 3, preferably a is 3, or
c) X는 [(CH2)nSiR3-a[(CH2)nSi(OH)R2]a]이고 a는 1 내지 3, 바람직하게는 a는 3이거나, 또는c) X is [(CH 2 ) n SiR 3-a [(CH 2 ) n Si (OH) R 2 ] a ] and a is 1 to 3, preferably a is 3, or
d) X는 [(CH2)nSiR3-a[(CH2)nSiR3-a[(CH2)nSi(OH)R2]a]a]이고 a는 1 내지 3, 바람직하게는 3이다].d) X is [(CH 2 ) n SiR 3-a [(CH 2 ) n SiR 3-a [(CH 2 ) n Si (OH) R 2 ] a ] a ] and a is 1 to 3, preferably Is 3].
[화학식 2][Formula 2]
[상기 식 중에서, [In the above formula,
n은 2 내지 6, 바람직하게는 n은 2이고, R은 C1-C18-알킬 및(또는) C6-C20-아릴 (여기서, n값 및 R기는 분자 내에서 같거나 다를 수 있음)이고,n is 2 to 6, preferably n is 2, and R is C 1 -C 18 -alkyl and / or C 6 -C 20 -aryl, wherein the n value and the R group can be the same or different in the molecule )ego,
추가의 기호 및 표시는 Additional symbols and signs are
A) K는 [R4-iSi] (여기서, i는 3 내지 4, 바람직하게는 4임)이거나, 또는A) K is [R 4-i Si], where i is 3 to 4, preferably 4; or
B) K는B) K is
(여기서, i는 m과 동일하며, 3 내지 6, 바람직하게는 i는 m과 동일하며 4임)이고Where i is equal to m and 3 to 6, preferably i is equal to m and is 4)
a) Y는 Cl, Br, I이고 a는 1이거나, 또는a) Y is Cl, Br, I and a is 1, or
b) Y는 [(CH2)nSi(Z)R2] (여기서, Z는 Cl, Br, I임)이고 a는 1 내지 3, 바람직하게는 a는 3이거나, 또는b) Y is [(CH 2 ) n Si (Z) R 2 ] where Z is Cl, Br, I and a is 1 to 3, preferably a is 3, or
c) Y는 [(CH2)nSiR3-a[(CH2)nSi(Z)R2]a] (여기서, Z는 Cl, Br, I임)이고 a는 1 내지 3, 바람직하게는 a는 3이거나, 또는c) Y is [(CH 2 ) n SiR 3-a [(CH 2 ) n Si (Z) R 2 ] a ] where Z is Cl, Br, I and a is 1 to 3, preferably A is 3, or
d) Y는 [(CH2)nSiR3-a[(CH2)nSiR3-a[(CH2)nSi(Z)R2]a]a] (여기서, Z는 Cl, Br, I임)이고 a는 1 내지 3, 바람직하게는 a는 3이다].d) Y is [(CH 2 ) n SiR 3-a [(CH 2 ) n SiR 3-a [(CH 2 ) n Si (Z) R 2 ] a ] a ] where Z is Cl, Br, I) and a is 1 to 3, preferably a is 3.
결과적으로, 반응은 2상 반응으로 수행되는데, 다시 말해서 화학식 2의 Si-할로겐 함유 카르보실란 덴드리머 (추출물) 및 화학식 1의 SiOH-관능성 카르보실란 덴드리머 (생성물)가 모두 용해되어 있는 유기상, 및 염기 및 반응 과정 중에 생성된 염이 용해되어 있는 수성상을 포함하는 2상 혼합물의 상 경계면에서 가수분해가 일어난다.As a result, the reaction is carried out in a two-phase reaction, that is, an organic phase in which both Si-halogen-containing carbosilane dendrimer (extract) of formula (2) and SiOH-functional carbosilane dendrimer (product) of formula (1) are dissolved, and a base And hydrolysis occurs at the phase interface of the biphasic mixture comprising an aqueous phase in which the salts generated during the reaction are dissolved.
물과 완전하게 섞이지 않는 모든 유기 용매 및(또는) 용매 혼합물을 본 발명의 취지에 속하는 유기상의 용매로 간주한다. 용매 혼합물은 임의로 단상이거나 다상일 수 있다. 지방족 에테르가 바람직하게 사용되며, 특히 바람직하게는 tert-부틸 메틸 에테르이다.All organic solvents and / or solvent mixtures that do not mix completely with water are considered to be solvents in the organic phase that fall within the spirit of the invention. The solvent mixture may optionally be single phase or multiphase. Aliphatic ethers are preferably used, particularly preferably tert-butyl methyl ether.
어떠한 수용성 염기 및 그의 혼합물 (예를 들면, NH3, 알칼리 금속 수산화물, 및 암모늄 및 알칼리 금속의 탄산염, 탄산 수소염, 인산염, 인산 수소염 및(또는) 아세트산염)이라도 본 발명의 취지에 속하는 염기로 사용될 수 있다. NH3, 알칼리 금속 수산화물, 알칼리 금속 탄산염 및(또는) 알칼리 금속 탄산 수소염이 바람직하게 사용되며, 특히 바람직하게는 NH3이다.Any water soluble base and mixtures thereof (eg, NH 3 , alkali metal hydroxides, and carbonates, hydrogen carbonates, phosphates, hydrogen phosphates and / or acetates of ammonium and alkali metals) are bases of the present invention. Can be used as NH 3 , alkali metal hydroxides, alkali metal carbonates and / or alkali metal hydrogen carbonates are preferably used, particularly preferably NH 3 .
염기는 가수분해에 의해 유리되는 산량에 대해 화학량론적인 양 또는 과량 사용하며, NH3이 염기인 경우에는 2 내지 10배 과량이 바람직하다.The base is used in a stoichiometric amount or in excess of the amount of acid liberated by hydrolysis, and a 2 to 10 fold excess is preferred when NH 3 is a base.
본 발명에 따른 방법은 0 ℃ 이상, 특히 바람직하게는 0 내지 50 ℃ 범위의 온도에서 수행하는 것이 바람직하다.The process according to the invention is preferably carried out at a temperature of at least 0 ° C, particularly preferably in the range from 0 to 50 ° C.
화학식 2의 화합물은 동시 계류 중인 미국 특허 출원 제08/785 463호에 대응하는 미국 특허 제5 677 410호 및 독일 특허 공개 제196 03 241호에 따라 히드로실릴화 반응, 다시 말해서 적당한 불포화 실란과 히드리도실란, 예를 들면 할로실란을 촉매 존재하에서 반응시킴으로서 바람직하게 제조할 수 있다.Compounds of formula (2) are hydrosilylation reactions, ie suitable unsaturated silanes and hydrides, according to US Pat. No. 5 677 410 and German Patent Publication No. 196 03 241 corresponding to co-pending US patent application Ser. Lidosilanes, for example, can be preferably produced by reacting halosilanes in the presence of a catalyst.
본 발명의 특히 바람직한 실시양태에는, 화학식 2의 카르보실란 덴드리머는 불포화 실란, 예를 들면, 테트라비닐 실란 및 시클로[테트라(메틸비닐 실록산)]과 할로히드리도실란, 예를 들면 클로로디메틸 실란을 균질 촉매, 바람직하게는 비닐기를 함유하는 실록산 매트릭스 중의 백금 착물 (예를 들면, 이소프로판올 중의 시클로[테트라(메틸비닐 실록산)] 리간드로 치환된 Pt 착물 68 % 용액인 실로프렌 U (Silopren U) 촉매 Pt/S) 존재하에서 반응시킴으로써 제조한다.In a particularly preferred embodiment of the invention, the carbosilane dendrimer of formula (2) is homogeneous to unsaturated silanes such as tetravinyl silane and cyclo [tetra (methylvinyl siloxane)] and halohydridosilanes such as chlorodimethyl silane. Silopren U catalyst Pt / which is a 68% solution of a Pt complex substituted with a platinum complex (e.g. a cyclo [tetra (methylvinyl siloxane)] ligand in isopropanol in a catalyst, preferably a siloxane matrix containing a vinyl group S) by making it react in presence.
만일, 히드로실릴화 반응이 본 발명에 따른 방법에 적당한 용매 중에서 미리 수행되었다면, 그 반응 중에 형성된 반응 생성물은 반응계내, 다시 말해서 추가의 처리를 하지 않고서도 사용될 수 있다.If the hydrosilylation reaction has previously been carried out in a solvent suitable for the process according to the invention, the reaction product formed during the reaction can be used in the reaction system, that is to say without further treatment.
본 발명에 따른 방법은 회분식, 예를 들면 교반 탱크 반응기, 및 연속 방식, 예를 들면, 관형 유통 반응기로 수행할 수 있다. 상기에 있어서, 적당한 용매, 바람직하게는 지방족 에테르, 특히 바람직하게는 tert-부틸메틸 에테르에 용해되어 있는 화학식 2의 카르보실란 덴드리머, 또는 임의로 히드로실릴화 반응의 반응 생성물을 2상 혼합물에 천천히 가하는 것이 바람직하며, 이때 수성상 및 유기상을 강력하게 혼합시키는 것이 바람직하다. 예를 들면, 이러한 혼합은 교반 탱크 혼합기에서는 강력한 교반으로, 또는 관형-유통 반응기에서는 난류로 수행될 수 있다.The process according to the invention can be carried out in a batch, for example a stirred tank reactor, and in a continuous mode, for example a tubular flow reactor. In the above, the slow addition of the reaction product of the carbosilane dendrimer of formula (2), or optionally hydrosilylation reaction, dissolved in a suitable solvent, preferably aliphatic ether, particularly preferably tert-butylmethyl ether, Preference is given to mixing the aqueous phase and the organic phase strongly. For example, this mixing can be carried out with vigorous stirring in a stirred tank mixer or turbulent flow in a tubular-flow reactor.
혼합은 상 경계면에서 반응이 일어나도록 만든다. 가수분해 중에 유리되는 산이 염기 또는 염기 혼합물과 반응하여, 수성상에 용해되는 염 또는 염 혼합물을 제공한다. 형성되는 화학식 1의 SiOH-관능성 카르보실란 덴드리머가 유기상에 용해된다. 반응 성분의 상이한 용해도 특성 및 침전물 형성의 제거로 인해, 생성물을 단순한 방식으로 분리하고 처리할 수 있다.Mixing causes the reaction to take place at the phase interface. The acid liberated during hydrolysis reacts with the base or base mixture to provide a salt or salt mixture that dissolves in the aqueous phase. The SiOH-functional carbosilane dendrimer of Formula 1 formed is dissolved in the organic phase. Due to the different solubility characteristics of the reaction components and the elimination of precipitate formation, the product can be separated and treated in a simple manner.
반응이 완료된 후에, 상을 분리하고, 만일 반응이 연속식이라면 경우에 따라 별도의 반응 용기 중에서 회분식으로 반응을 수행한다.After the reaction is complete, the phases are separated and if the reaction is continuous, the reaction is carried out batchwise in a separate reaction vessel as the case may be.
수성상을 분리하는 것이 바람직하며, 유기상은 물 또는 염, 염기 또는 산의 수용액으로 1회 이상 세척하고, 필요에 따라 잔류의 물을, 예를 들면 무수 알칼리 금속 황산염, 알칼리 토금속 황산염, 염화 칼슘으로 건조시키고(거나) 분자체 또는 증류 공정으로 제거한다.It is preferable to separate the aqueous phase, and the organic phase is washed one or more times with an aqueous solution of water or a salt, a base or an acid, and if necessary, the residual water is washed with, for example, anhydrous alkali metal sulfate, alkaline earth metal sulfate, calcium chloride. Dry and / or remove by molecular sieve or distillation process.
형성되는 화학식 1의 SiOH-관능성 카르보실란 덴드리머는 휘발성 성분을 제거시킴으로써, 예를 들면 응축 또는 증류시킴으로써 고체 또는 오일로서 분리할 수 있다. 만일, 생성물이 고체라면, 생성물을 용해시키지 않거나 또는 약간만을 용해시키는 용매 (침전제) 또는 용매 혼합물에 유기상을 가하여 분산시키고, 이어서 여과시키는 직접적인 방식으로 분리할 수 있다. 적당한 용매에는, 예를 들면 시클릭, 지방족 또는 방향족 탄화수소 (예를 들면, 시클로헥산, 펜탄, 헥산, 헵탄, 톨루엔 및(또는) 크실렌)가 있다. 또한, 침전제를 유기상에 가할 수도 있다.The SiOH-functional carbosilane dendrimers of formula (1) formed can be isolated as solids or oils by removing volatile components, for example by condensation or distillation. If the product is a solid, it can be separated in a direct manner by adding an organic phase to a solvent (precipitant) or solvent mixture which does not dissolve or only slightly dissolves the product, which is then filtered. Suitable solvents are, for example, cyclic, aliphatic or aromatic hydrocarbons (eg cyclohexane, pentane, hexane, heptane, toluene and / or xylene). In addition, a precipitant may be added to the organic phase.
만일, 생성물이 용해된 형태로 추가로 반응하거나, 소정 용도에 제공되는 경우에는, 생성물의 분리를 생략하고, 유기상을 직접적인 방식으로 사용할 수 있다. 다른 처리 단계도 가능하며, 예를 들면 바람직한 고비점 용매를 가하고, 이어서 원용매 또는 용매 혼합물을 제거시키기 위해 증류 또는 응축시킴으로서 용매를 교환할 수 있다.If the product is further reacted in dissolved form or provided for a given use, separation of the product can be omitted and the organic phase can be used in a direct manner. Other processing steps are possible, for example, by exchanging the solvent by adding a preferred high boiling solvent followed by distillation or condensation to remove the raw solvent or solvent mixture.
본 발명에 따른 방법을 하기의 실시예에 설명하였으나, 이것으로 본 발명을 한정하려는 것은 아니다.Although the method according to the invention has been described in the following examples, this is not intended to limit the invention.
〈실시예〉<Example>
하기의 가수분해 후의 처리 단계를 제외하고는, 모든 반응을 보호 가스 (아르곤) 대기하에서 수행하였다.All reactions were carried out under a protective gas (argon) atmosphere except for the following treatment steps after hydrolysis.
tert-부틸메틸 에테르 (이하에서는 약자 TBME로 칭함) (H2O 함량 ＜0.05 %), n-헥산, 디에틸 에테르, 테트라비닐 실란, 시클로[테트라(메틸 비닐 실록산)], 클로로디메틸 실란, NaHCO3, Na2CO3, NaOH, NaCl 및 Na2SO4를 추가의 처리를 하지 않고서 시판 생성물로서 직접 사용하였다. NH3 수용액은 25 %의 NH3 수용액을 희석하여 제조하였다.tert-butylmethyl ether (hereinafter abbreviated TBME) (H 2 O content <0.05%), n-hexane, diethyl ether, tetravinyl silane, cyclo [tetra (methyl vinyl siloxane)], chlorodimethyl silane, NaHCO 3 , Na 2 CO 3 , NaOH, NaCl and Na 2 SO 4 were used directly as commercial products without further treatment. NH 3 aqueous solution was prepared by diluting 25% aqueous NH 3 solution.
불균일 촉매 1 (Pt 함량 1 %)을 미국 특허 제5 677 410호의 실시예 8에 따라 분말 활성탄을 H2PtCl6로 코팅시킴으로써 제조하였다.Heterogeneous catalyst 1 (Pt content 1%) was prepared by coating powdered activated carbon with H 2 PtCl 6 according to Example 8 of US Pat. No. 5,677,410.
실로프렌 U 촉매 Pt/S (이소프로판올 중의 시클로[테트라(메틸비닐 실록산)]리간드로 치환된 Pt 착물 68 % 용액)을 바이엘 아게 (Bayer AG) (독일)로부터 구입하였다.Siloprene U catalyst Pt / S (68% solution of Pt complex substituted with cyclo [tetra (methylvinyl siloxane)] ligand in isopropanol) was purchased from Bayer AG (Germany).
1H-NMR 측정은 400 MHz에서 수행하였다. 1 H-NMR measurements were performed at 400 MHz.
실시예 1Example 1
출발 화합물 Si[(CH2)2Si(CH3)2Cl]4의 제법Preparation of Starting Compound Si [(CH 2 ) 2 Si (CH 3 ) 2 Cl] 4
합성법은 미국 특허 제5 677 410호에 기재된 바와 같다.Synthesis is as described in US Pat. No. 5,677,410.
아르곤 하에서, 클로로디메틸 실란 234.2 g (2.475 mol), TBME 500 ㎖ 및 촉매 1 1.5 g을 테트라비닐 실란 75 g (0.550 mol)에 가하였다. 반응 혼합물을 발열 반응이 발생할 때까지 세차게 교반하면서 45 ℃로 가열하였고, 온도가 51 ℃로 상승되었다. 그 뒤, 테트라비닐 실란 525 g (3.853 mol), 클로로디메틸 실란 1639.4 g (17.327 mol) 및 TBME 940 ㎖을 포함하는 혼합물을 천천히 적가하였고, 이때 반응 온도가 50 ℃ 미만으로 떨어지지 않게 주의했다. 그 뒤, 환류하에서 1.5 시간동안 교반을 지속하고, 반응 혼합물을 실온으로 냉각시키고, 촉매를 프릿 (frit)을 통해 여과 제거하고, 휘발성 성분을 감압 하에서 무색 용액으로부터 제거하였다. 생성물은 백색 고체 형태였다.Under argon, 234.2 g (2.475 mol) of chlorodimethyl silane, 500 mL of TBME and 1.5 g of catalyst 1 were added to 75 g (0.550 mol) of tetravinyl silane. The reaction mixture was heated to 45 ° C. with vigorous stirring until an exothermic reaction occurred and the temperature was raised to 51 ° C. Thereafter, a mixture containing 525 g (3.853 mol) of tetravinyl silane, 1639.4 g (17.327 mol) of chlorodimethyl silane and 940 ml of TBME was slowly added dropwise, taking care not to drop the reaction temperature below 50 ° C. Stirring was then continued for 1.5 hours under reflux, the reaction mixture was cooled to room temperature, the catalyst was filtered off through frit and the volatile components were removed from the colorless solution under reduced pressure. The product was in the form of a white solid.
수득량 : 2120.8 g (이론적인 수득량의 94 %)Yield: 2120.8 g (94% of theoretical yield)
실시예 2Example 2
염기로서 NH3를 사용하는 Si[(CH2)2Si(CH3)2OH]4의 합성법Synthesis of Si [(CH 2 ) 2 Si (CH 3 ) 2 OH] 4 using NH 3 as a base
배출 코크가 달린 10 L의 평면 플랜지 용기에 TBME 2.6 L (1924 g) 및 NH3 473.5 g (27.8 mol)을 함유하는 NH3 수용액 2894 g을 아르곤 하에 놓았다. 세차게 교반하여 2상을 강력하게 혼합시키면서, Si[(CH2)2Si(CH3)2Cl]4 (실시예 1로부터 얻음) 720 g (1.399 mol)을 건조된 TBME 800 ㎖ (592 g)에 천천히 적가하며, 이때 반응 온도가 38 ℃로 천천히 상승되었다. 적가한 후에, 실온에서 1.5 시간 동안, 교반을 지속하고, 그 후 상분리시키고, 유기상을 매번 3 L의 물로 2회 세척하고, Na2SO4로 건조시켰다. 건조제를 여과 제거한 후, 유기상을 10 L의 n-헥산에 적가하여, 이때 생성물이 미세한 결정질 백색 고체로 침강되었고, 이를 여과하고, 30 ℃의 감압 하에서 건조시켰다.Release the NH 3 aqueous solution 2894 g containing TBME 2.6 L (1924 g) and NH 3 473.5 g (27.8 mol) on the flat flange vessel of 10 L with a discharge cock under argon. While stirring vigorously to mix the two phases vigorously, 720 g (1.399 mol) of Si [(CH 2 ) 2 Si (CH 3 ) 2 Cl] 4 (obtained from Example 1) were added 800 ml (592 g) of dried TBME. Was slowly added dropwise, at which time the reaction temperature rose slowly to 38 ° C. After the dropwise addition, stirring was continued for 1.5 hours at room temperature, followed by phase separation, and the organic phase was washed twice with 3 L of water each time and dried over Na 2 SO 4 . After the drying agent was filtered off, the organic phase was added dropwise to 10 L of n-hexane, at which time the product precipitated into a fine crystalline white solid, which was filtered and dried under reduced pressure at 30 ° C.
(TBME/H2O의 중량비 : 1.04)(Weight ratio of TBME / H 2 O: 1.04)
수득량 : 464.7 g (이론적인 수득량의 75.4 %)Yield: 464.7 g (75.4% of theoretical yield)
C16H44O4Si5 C 16 H 44 O 4 Si 5
M = 440.95 g/molM = 440.95 g / mol
융점 : 142 내지 143 ℃Melting Point: 142-143 ° C
1H-NMR (DMSO-d6) : 0.0 ppm (s, 6H, Si(CH3)); 0.38 ppm (m, 4H, Si(CH2)2Si); 5.22 ppm (s, 1H, Si(OH)). 1 H-NMR (DMSO-d 6 ): 0.0 ppm (s, 6H, Si (CH 3 )); 0.38 ppm (m, 4H, Si (CH 2 ) 2 Si); 5.22 ppm (s, 1H, Si (OH)).
실시예 3Example 3
염기로서 NaHCO3를 사용하는 Si[(CH2)2Si(CH3)2OH]4의 합성법Synthesis method of Si [(CH 2 ) 2 Si (CH 3 ) 2 OH] 4 using NaHCO 3 as a base
TBME 50 ㎖ (37 g) 중에 용해되어 있는 Si[(CH2)2Si(CH3)2Cl]4 (실시예 1로부터 얻음) 10 g (19.4 mmol)을, H2O 200 ㎖ 및 TBME 200 ㎖ (148 g) 중의 NaHCO3 16.38 g (195 mmol) 용액을 포함하는 세차게 교반된 혼합물에 실온에서 천천히 적가하여, 이때 온도가 28 ℃로 상승하였다. 그 뒤, 1시간 동안 교반을 지속하고, 유기상을 분별 깔대기로 분리시키고, Na2SO4로 건조시켰다. 건조제를 여과 제거한 후에, 유기상을 1 L의 n-헥산에 적가하고, 이때 생성물은 미세한 결정질 백색 고체로서 침강되고, 이를 여과하고, 30 ℃의 감압 하에서 건조시켰다.10 g (19.4 mmol) of Si [(CH 2 ) 2 Si (CH 3 ) 2 Cl] 4 (obtained from Example 1) dissolved in 50 mL (37 g) of TBME was dissolved in 200 mL of H 2 O and TBME 200 To a vigorously stirred mixture containing 16.38 g (195 mmol) solution of NaHCO 3 in mL (148 g) was slowly added dropwise at room temperature, at which time the temperature rose to 28 ° C. Agitation was then continued for 1 hour, the organic phase was separated with a separatory funnel and dried over Na 2 S0 4 . After the drying agent was filtered off, the organic phase was added dropwise to 1 L of n-hexane, at which time the product precipitated as a fine crystalline white solid, which was filtered and dried under reduced pressure at 30 ° C.
(TBME/H2O의 중량비 : 0.93)(Weight ratio of TBME / H 2 O: 0.93)
수득량 : 5.2 g (이론적인 수득량의 60.7 %)Yield: 5.2 g (60.7% of theoretical yield)
융점 : 141 내지 142 ℃Melting Point: 141 to 142 ° C
실시예 4Example 4
염기로서 Na2CO3를 사용하는 Si[(CH2)2Si(CH3)2OH]4의 합성법Synthesis of Si [(CH 2 ) 2 Si (CH 3 ) 2 OH] 4 using Na 2 CO 3 as base
H2O 1000 ㎖ 및 TBME 1000 ㎖ (740 g) 중에 Na2CO3 30.94 g (292 mmol)을 실온에서 용해시키고, TBME 250 ㎖ (185 g) 중의 Si[(CH2)2Si(CH3)2Cl]4 (실시예 1로부터 얻음) 50 g (97.1 mmol)을 세차게 교반된 혼합물에 아르곤 하에서 적가하였다. 그 뒤, 1시간 동안 교반을 지속하고, 유기상을 분리하고, Na2SO4로 건조시킨 후, 5 L의 n-헥산에 적가하여, 이때 생성물이 미세한 결정질의 백색 고체로서 침강되었고, 이를 여과하고, 30 ℃의 감압 하에서 건조시켰다.30.94 g (292 mmol) of Na 2 CO 3 in 1000 mL of H 2 O and 1000 mL (740 g) of TBME were dissolved at room temperature and Si [(CH 2 ) 2 Si (CH 3 ) in 250 mL (185 g) TBME. 2 Cl] 4 (from Example 1) 50 g (97.1 mmol) were added dropwise under argon to the vigorously stirred mixture. Then, stirring was continued for 1 hour, the organic phase was separated, dried over Na 2 SO 4 , and added dropwise to 5 L of n-hexane, where the product precipitated as a fine crystalline white solid, which was filtered and And dried under reduced pressure at 30 ° C.
(TBME/H2O의 중량비 : 0.93)(Weight ratio of TBME / H 2 O: 0.93)
수득량 : 33.1 g (이론적인 수득량의 77.3 %)Yield: 33.1 g (77.3% of theoretical yield)
융점 : 142 내지 143 ℃Melting Point: 142-143 ° C
실시예 5Example 5
염기로서 Na2CO3 및 NaOH를 사용하는 Si[(CH2)2Si(CH3)2OH]4의 합성법Synthesis of Si [(CH 2 ) 2 Si (CH 3 ) 2 OH] 4 using Na 2 CO 3 and NaOH as base
TBME 50 ㎖ (37 g) 중의 Si[(CH2)2Si(CH3)2Cl]4 (실시예 1로부터 얻음) 10 g (19.4 mmol)을 H2O 200 ㎖ 및 TBME 200 ㎖ (148 g) 중의 NaOH 2.34 g (58.5 mmol) 및 Na2CO3 1.55 g (14.6 mmol) 용액을 포함하는, 세차게 교반된 혼합물에 실온의 아르곤 하에서 적가하고, 1시간 동안 교반을 지속하고, 유기상을 분리하고, Na2SO4로 건조시키고, n-헥산 1000 ㎖에 적가하여, 이때 생성물이 백색 고체로서 침강되었다. 이를 여과하고, 70 ℃에서 건조시켰다.10 g (19.4 mmol) of Si [(CH 2 ) 2 Si (CH 3 ) 2 Cl] 4 (obtained from Example 1) in 50 mL (37 g) of TBME was charged with 200 mL of H 2 O and 200 mL (148 g) of TBME. To a vigorously stirred mixture containing 2.34 g (58.5 mmol) of NaOH and 1.55 g (14.6 mmol) solution of Na 2 CO 3 in ) was added dropwise under argon at room temperature, the stirring was continued for 1 hour, the organic phase was separated, Dried over Na 2 SO 4 and added dropwise to 1000 ml n-hexane, at which time the product precipitated as a white solid. It was filtered and dried at 70 ° C.
수득량 : 6.3 g (이론적인 수득량의 73.5 %)Yield: 6.3 g (73.5% of theoretical yield)
(TBME/H2O의 중량비 : 0.93)(Weight ratio of TBME / H 2 O: 0.93)
융점 : 141 내지 142 ℃Melting Point: 141 to 142 ° C
실시예 6Example 6
염기로서 NH3를 사용하는 Si[(CH2)2Si(CH3)2OH]4의 합성법Synthesis of Si [(CH 2 ) 2 Si (CH 3 ) 2 OH] 4 using NH 3 as a base
테트라비닐 실란 200 g (1.468 mol), TBME 480 ㎖ (355.2 g) 및 실로프렌 U 촉매 Pt/S 0.1 ㎖을 보호 가스 대기하에 두었고, (CH3)2SiHCl 총 556 g (5.876 mol)을 교반하면서 적가하였다. 반응을 개시하기 위해, (CH3)2SiHCl 약 30 ㎖를 우선 실온에서 빠르게 가하여, 이때 발열 반응이 일어나는 결과로서 온도가 약 32 ℃로 상승하였다. 나머지 (CH3)2SiHCl를 온도가 연속적으로 약 60 ℃까지 상승되게 하는 비율로 적가하였다. 그 뒤, 환류하에서 2시간 동안 계속 가열하였다. 실온으로 냉각될 때, 반응 혼합물을 TBME 300 ㎖ (222 g)으로 희석시키고, 1.5 시간내에 H2O 2900 ㎖ 및 TBME 2600 ㎖ (1924 g) 중의 NH3 473.5 g (27.8 mol)을 포함하는 세차게 교반된 혼합물에 적가하였다. 그 뒤, 1시간 동안 교반을 지속하고, 수성상을 분리하고, 유기상을 매번 H2O 1000 ㎖로 2회 세척한 뒤, Na2SO4로 건조시켰다. 건조제를 여과 제거한 후에, 유기상을 10 L의 n-헥산에 적가하여, 이때 생성물이 백색 고체로서 침강되었고, 이를 여과하고 30 ℃의 감압 하에서 건조시켰다.200 g (1.468 mol) of tetravinyl silane, 480 ml (355.2 g) of TBME and 0.1 ml of siloprene U catalyst Pt / S were placed under protective gas atmosphere and a total of 556 g (5.876 mol) of (CH 3 ) 2 SiHCl were stirred. Added dropwise. To initiate the reaction, about 30 mL of (CH 3 ) 2 SiHCl was first rapidly added at room temperature, at which time the temperature rose to about 32 ° C. as a result of the exothermic reaction taking place. The remaining (CH 3 ) 2 SiHCl was added dropwise at a rate such that the temperature was continuously raised to about 60 ° C. Then heating was continued for 2 hours under reflux. When cooled to room temperature, the reaction mixture is diluted with 300 mL (222 g) of TBME and vigorously stirred with 1.53.5 g (27.8 mol) of NH 3 in 2600 mL of H 2 O and 2600 mL (1924 g) of TBME in 1.5 h. To the prepared mixture. Then stirring was continued for 1 hour, the aqueous phase was separated and the organic phase was washed twice with 1000 ml of H 2 O each time and then dried over Na 2 SO 4 . After the drying agent was filtered off, the organic phase was added dropwise to 10 L of n-hexane, at which time the product precipitated as a white solid, which was filtered and dried under reduced pressure at 30 ° C.
(TBME/H2O의 중량비 : 0.86)(Weight ratio of TBME / H 2 O: 0.86)
수득량 : 359 g (테트라비닐 실란에 대한 이론적인 수득량의 55.5 %)Yield: 359 g (55.5% of the theoretical yield for tetravinyl silane)
융점 : 141 내지 143 ℃ Melting Point: 141 to 143 ° C
실시예 7Example 7
염기로서 NH3을 사용하는 Si[(CH2)2Si(CH3)2OH]4의 합성법Synthesis of Si [(CH 2 ) 2 Si (CH 3 ) 2 OH] 4 using NH 3 as a base
테트라비닐 실란 25 g (183 mmol) 및 (CH3)2SiHCl 69.9 g (739 mmol)의 혼합물을 TBME 170 ㎖ (125.8 g) 및 실로프렌 U 촉매 Pt/S의 출발 충전물에 보호 가스 대기하에서 및 환류되도록 가열하면서 적가하였다. 그 뒤, 1시간 동안 환류하에서 교반을 지속하고, 반응 혼합물을 실온으로 냉각시키고, TBME 430 ㎖ (318.2 g) 및 NH3 60.8 g (3.576 mol)을 함유하는 수용액 400 g을 포함하는 세차게 교반된 혼합물에 적가하였다. 그 뒤, 1시간 동안 교반을 지속하고, 이어서 수성상을 분리하고 유기상을 H2O 400 ㎖ 및 농축 NaCl 수용액 400 ㎖으로 각각 1회 세척하고, Na2SO4로 건조시키고, n-헥산 1100 ㎖에 적가하였다. 침강된 고체를 여과하고, 30 ℃의 감압 하에서 건조시켰다.A mixture of 25 g (183 mmol) of tetravinyl silane and 69.9 g (739 mmol) of (CH 3 ) 2 SiHCl was added to 170 mL (125.8 g) TBME and starting charge of siloprene U catalyst Pt / S under reflux gas atmosphere and at reflux. It was added dropwise while heating. Then, stirring was continued under reflux for 1 hour, the reaction mixture was cooled to room temperature, and the stirred mixture was mixed with 400 g of an aqueous solution containing 430 ml (318.2 g) of TBME and 60.8 g (3.576 mol) of NH 3. Was added drop wise. Then, stirring was continued for 1 hour, then the aqueous phase was separated and the organic phase was washed once with 400 ml of H 2 O and 400 ml of concentrated aqueous NaCl solution, respectively, dried over Na 2 SO 4 , and 1100 ml of n-hexane. Was added drop wise. The precipitated solid was filtered off and dried under reduced pressure at 30 ° C.
(TBME/H2O의 중량비 : 1.31)(Weight ratio of TBME / H 2 O: 1.31)
수득량 : 54.8 g (테트라비닐 실란에 대한 이론적인 수득량의 67.8 %)Yield: 54.8 g (67.8% of the theoretical yield for tetravinyl silane)
융점 : 142 내지 143 ℃Melting Point: 142-143 ° C
실시예 8Example 8
염기로서 NH3를 사용한 시클로-{OSi(CH3)[(CH2)2Si(CH3)2(OH)]}4의 합성법Synthesis of cyclo- {OSi (CH 3 ) [(CH 2 ) 2 Si (CH 3 ) 2 (OH)]} 4 with NH 3 as a base
(CH3)2SiHCl 788 g (8.33 mol)을 시클로-{OSi(CH3)(C2H3)}4 689 g (2 mol), TBME 1200 ㎖ (888 g) 및 실로프렌 U 촉매 Pt/S 0.2 ㎖을 포함하는 혼합물에 45 ℃에서 교반하면서 적가하였다. 이 첨가 동안, 반응 온도가 60 ℃으로 연속적으로 상승되었다. 첨가를 완료한 후, 환류하에서 1시간 동안 계속 가열하고, 반응 혼합물을 실온으로 냉각시키고, TBME 3000 ㎖ (2220 g) 및 NH3 681 g (40 mol)이 함유된 NH3 수용액 3750 g을 포함하는 세차게 혼합된 2상 혼합물에 천천히 적가하였다. 그 뒤, 실온에서 1시간 동안 교반을 지속하고, 상분리시키고, 유기상을 H2O 3500 ㎖ 및 약 5 %의 NaCl 용액 3500 ㎖으로 각각 1회씩 세척하고, Na2SO4로 건조시켰다.788 g (8.33 mol) of (CH 3 ) 2 SiHCl was dissolved in cyclo- {OSi (CH 3 ) (C 2 H 3 )} 4 689 g (2 mol), TBME 1200 ml (888 g) and siloprene U catalyst Pt / To the mixture containing 0.2 ml of S was added dropwise with stirring at 45 ° C. During this addition, the reaction temperature was continuously raised to 60 ° C. After the addition was complete, heating continued for one hour at reflux, the reaction mixture was cooled to room temperature, TBME 3000 ㎖ (2220 g) and NH 3 681 g (40 mol) containing NH 3 aqueous solution of 3750 g is contained It was slowly added dropwise to the vigorously mixed biphasic mixture. Stirring was then continued for 1 hour at room temperature, the phases were separated, and the organic phase was washed once each with 3500 mL of H 2 O and 3500 mL of about 5% NaCl solution and dried over Na 2 SO 4 .
건조제를 여과 제거시킨 후, 휘발성 성분을 25 ℃의 감압 하에서 응축시켰다. 여전히 약 5 %의 TBME를 함유하는 투명한 연황색의 고점도 오일을 수득하였다.After the drying agent was filtered off, the volatile components were condensed under reduced pressure at 25 ° C. A clear pale yellow high viscosity oil still containing about 5% TBME was obtained.
(TBME/H2O의 중량비 : 1.01)(Weight ratio of TBME / H 2 O: 1.01)
수득량 : 오일 1294 g (이론적인 수득량 : 1296.4 g)Yield: 1294 g of oil (theoretical yield: 1296.4 g)
1H-NMR (DMSO-d6) : = 0.0 ppm (s, 6H, Si(CH3)2); 0.08 ppm (s, 3H, Si(CH3)); 0.43 ppm (m, 4H, Si(CH2)2Si); 5.25 ppm (s, 1H, Si(OH)). 1 H-NMR (DMSO-d 6 ): = 0.0 ppm (s, 6H, Si (CH 3 ) 2 ); 0.08 ppm (s, 3H, Si (CH 3 )); 0.43 ppm (m, 4H, Si (CH 2 ) 2 Si); 5.25 ppm (s, 1H, Si (OH)).
비교예 1 : (미국 특허 제5 677 410호에 따름) Comparative Example 1 : According to US Patent No. 5 677 410
Si[(CH2)2Si(CH3)2OH]4의 합성법Synthesis method of Si [(CH 2 ) 2 Si (CH 3 ) 2 OH] 4
Si[(CH2)2Si(CH3)2Cl]4 94.3 g (183.4 mmol)을 디에틸 에테르 (Et2O) 100 ㎖ (70.8 g)에 용해시키고, 실온에서 트리에틸아민 110.3 ㎖ (729.3 mmol), H2O 15.3 g (850 mmol) 및 TBME 3630 ㎖ (2686.2 g) 용액에 세차게 교반하면서 적가하였다. 트리에틸아민 염산염이 형성되어, 바로 커다란 백색 침전물로서 침강되었다. 반응 온도가 25 ℃ 내지 30 ℃가 되도록 적가를 빠르게 수행하였다. 첨가를 완료한 후, 1시간 동안 교반을 지속하고, 매번 TBME 500 ㎖로 2회 세척한 침전물을 프릿을 통과시켜 여과하였다. 휘발성 성분을 약 35 ℃의 감압 하에서 제거시킨 후, 백색 고체로서의 조 생성물을 여과물로부터 수득하였다. 이를 THF 120 ㎖에 용해시키고, 3 L의 헥산에 세차게 교반하면서 적가하였다. 미세한 백색 침전물을 여과하고, 헥산으로 세척한 뒤, 감압 하에서 건조시켰다.94.3 g (183.4 mmol) of Si [(CH 2 ) 2 Si (CH 3 ) 2 Cl] 4 are dissolved in 100 mL (70.8 g) of diethyl ether (Et 2 O), and 110.3 mL (729.3) of triethylamine at room temperature. mmol), H 2 O 15.3 g (850 mmol) and 3630 mL (2686.2 g) TBME solution were added dropwise with vigorous stirring. Triethylamine hydrochloride was formed and precipitated immediately as a large white precipitate. The dropwise addition was rapidly carried out so that the reaction temperature was 25 ° C to 30 ° C. After the addition was completed, stirring was continued for 1 hour, and the precipitate washed twice with 500 ml of TBME each time was filtered through a frit. After the volatile components were removed under reduced pressure at about 35 ° C., the crude product as a white solid was obtained from the filtrate. It was dissolved in 120 mL of THF and added dropwise to 3 L of hexane with vigorous stirring. The fine white precipitate was filtered off, washed with hexane and dried under reduced pressure.
((TBME + Et2O)/H2O의 중량비 : 180.2)(Weight ratio of (TBME + Et 2 O) / H 2 O: 180.2)
수득량 : 40.5 g (이론적인 수득량의 50.2 %)Yield: 40.5 g (50.2% of theoretical yield)
융점 : 139 내지 141 ℃Melting Point: 139 to 141 ℃
비교예 2Comparative Example 2
출발 생성물, 시클로-{SiO(CH3)[(CH2)2SiCl(CH3)2]}4 (동시 계류 중인 미국 특허 출원 제08/785463호에 대응하는 독일 특허 공개 제19603241호 중의 실시예 6과 유사함)의 합성법Starting product, cyclo- {SiO (CH 3 ) [(CH 2 ) 2 SiCl (CH 3 ) 2 ]} 4 (Examples in German Patent Publication No. 19603241 corresponding to co-pending US patent application Ser. No. 08/785463. Similar to 6)
클로로디메틸실란 69 g (726.7 mmol) 및 촉매 Cat 1 800 ㎎을 THF 120 ㎖ 중의 시클로-{SiO(CH3)(C2H3)]}4 50 g (145.2 mmol)에 교반하면서 도입하였다. 반응 혼합물을 50 ℃로 가열하였고, 이 온도에서 2시간이 경과한 후에도 열의 방출이 관찰되지 않았다. 55 내지 60 ℃에서 추가의 20 시간 경과후에, 혼합물을 실온으로 냉각하고, 촉매를 양면 프릿에 통과시켜 여과하였다. 투명한 무색의 침전물에서 휘발성 성분을 감압하에서 제거하여, 무색 오일 형태로 생성물을 수득하였다.69 g (726.7 mmol) of chlorodimethylsilane and 800 mg of catalyst Cat 1 were introduced into 50 g (145.2 mmol) of cyclo- {SiO (CH 3 ) (C 2 H 3 )]} 4 in 120 mL of THF with stirring. The reaction mixture was heated to 50 ° C. and no heat release was observed after 2 hours at this temperature. After an additional 20 hours at 55-60 ° C., the mixture was cooled to room temperature and the catalyst was filtered through a double sided frit. The volatile components in the clear colorless precipitate were removed under reduced pressure to give the product in the form of a colorless oil.
시클로-{OSi(CH3)[(CH2)2Si(CH3)2(OH)]}4의 합성법Synthesis of cyclo- {OSi (CH 3 ) [(CH 2 ) 2 Si (CH 3 ) 2 (OH)]} 4
디에틸 에테르 (Et2O) 100 ㎖ (70.8 g) 중의 시클로-{OSi(CH3)[(CH2)2SiCl(CH3)2)]}4 (상기에 기재한 바와 같이 제조됨) 105 g (145.2 mmol)을 트리에틸아민 87.4 ㎖ (63.6 g; 628.3 mmol), H2O 12.1 ㎖ (12.1 g; 672.2 mmol) 및 TBME 2850 ㎖ (2109 g)을 포함하는 혼합물에 1시간 동안 적가하였다. 첨가를 완료한 후에, 1시간 동안 교반을 지속하고, 커다란 트리에틸아민 염산염 침전물을 여과하였다. 침전물을 매번 TBME 400 ㎖로 2회 세척한 후에, 휘발성 성분을 회전 필름 증발기를 이용하여 감압 하에서 제거시키고, 오일성 잔류물을 THF 약 50 ㎖에 흡수시키고, 실리카겔 상에서 여과하였다. 모든 휘발성 성분을 감압 하에서 1회 이상 제거시킨 후, 점성유로서의 생성물을 수득하였다.Cyclo- {OSi (CH 3 ) [(CH 2 ) 2 SiCl (CH 3 ) 2 )]} 4 (prepared as described above) in 100 mL (70.8 g) diethyl ether (Et 2 O) 105 g (145.2 mmol) was added dropwise to the mixture comprising 87.4 mL (63.6 g; 628.3 mmol), 12.1 mL (12.1 g; 672.2 mmol) H 2 O and 2850 mL (2109 g) TBME for 1 hour. After the addition was complete, stirring was continued for 1 hour and the large triethylamine hydrochloride precipitate was filtered off. After washing the precipitate twice with 400 ml of TBME each time, the volatile components were removed under reduced pressure using a rotary film evaporator, and the oily residue was taken up in about 50 ml of THF and filtered over silica gel. After all the volatile components were removed at least once under reduced pressure, the product as a viscous oil was obtained.
((TBME + Et2O)/H2O의 중량비 : 180.1)((TBME + Et 2 O) / H 2 O weight ratio: 180.1)
수득량 : 오일 64.3 g (이론적인 수득량 : 94.1 g)Yield: 64.3 g of oil (theoretical yield: 94.1 g)
본 발명은 덴드리머의 생성 과정 중에 형성된 부산물이 제거하기가 어렵고, 이 부산물에 의해 반응 혼합물의 균일한 혼합이 지연되거나 방해되어 SiOH-관능성 카르보실란 덴드리머의 공업적 제조에 바람직하지 못한 단점이 있었던 기존의 방식을 부산물과 생성물의 상이한 용해도 특성을 이용하여 보완한 효과를 제공한다.The present invention is difficult to remove the by-products formed during the production of the dendrimer, by which the uniform mixing of the reaction mixture is delayed or hindered by the by-products, which has an undesirable disadvantage in the industrial production of SiOH-functional carbosilane dendrimer The method provides a complementary effect using different solubility characteristics of by-products and products.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19711650A DE19711650C1 (en) | 1997-03-20 | 1997-03-20 | Hydroxy-silyl-functional carbo-silane dendrimer preparation in good yield with easy separation from by-product |
| DE19711650.7 | 1997-03-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR19980080458A KR19980080458A (en) | 1998-11-25 |
| KR100492216B1 true KR100492216B1 (en) | 2005-09-26 |
Family
ID=7824034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR10-1998-0009454A KR100492216B1 (en) | 1997-03-20 | 1998-03-19 | Process for The Preparation of SiOH-Functional Carbosilane Dendrimers |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5880305A (en) |
| EP (1) | EP0866086B1 (en) |
| JP (1) | JPH10265483A (en) |
| KR (1) | KR100492216B1 (en) |
| DE (2) | DE19711650C1 (en) |
| RU (1) | RU2193576C2 (en) |
| TW (1) | TW446724B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10839321B2 (en) * | 1997-01-06 | 2020-11-17 | Jeffrey Eder | Automated data storage system |
| JP4383555B2 (en) * | 1998-05-29 | 2009-12-16 | 東レ・ダウコーニング株式会社 | Carbosiloxane dendrimer |
| DE19824188A1 (en) * | 1998-05-29 | 1999-12-02 | Bayer Ag | Aqueous preparation for the treatment of mineral building materials |
| US6184407B1 (en) | 1998-05-29 | 2001-02-06 | Dow Corning Toray Silicone Co., Ltd. | Carbosiloxane dendrimers |
| DE19828256A1 (en) * | 1998-06-25 | 1999-12-30 | Bayer Ag | Antifouling agents, a process for their production and use, and antifouling coatings made therefrom |
| EP0976775B1 (en) * | 1998-07-31 | 2005-10-12 | Dow Corning Toray Silicone Company, Ltd. | Carbosiloxane dendrimers |
| DE19860364C2 (en) * | 1998-12-24 | 2001-12-13 | 3M Espe Ag | Polymerizable dental materials based on siloxane compounds capable of curing, their use and manufacture |
| US6617039B1 (en) | 1999-06-16 | 2003-09-09 | Bayer Aktiengesellschaft | Nitrogen-free compounds as adhesion promoters for silicon-based scratch-resistant coatings on polycarbonate |
| DE10018429A1 (en) | 2000-04-14 | 2001-10-18 | Bayer Ag | Plastics that are stabilized with zinc oxide-containing, abrasion-resistant multi-layers |
| DE10102739A1 (en) | 2001-01-23 | 2002-07-25 | Bayer Ag | Production of sol-gel condensates e.g. for scratch-resistant coating materials for cars, involves reacting aqueous silica sol with silicon alkoxide and then with a polyfunctional organosilane |
| DE10103027A1 (en) | 2001-01-24 | 2002-07-25 | Bayer Ag | Adhesion promoter, e.g. for improving adhesion of silicon-based protective coatings to polymeric substrates, comprising two-component polyurethane binder based on alkoxysilane-modified polyisocyanate |
| DE10225825A1 (en) * | 2002-06-11 | 2004-01-08 | Bayer Ag | Multifunctional carbosiloxanes with linear and cyclic structural elements |
| US9107426B2 (en) * | 2012-03-26 | 2015-08-18 | Weiler And Company, Inc. | Separation chambers for deboning machines |
| RU2679633C1 (en) * | 2018-06-15 | 2019-02-12 | Федеральное государственное автономное образовательное учреждение высшего образования "Дальневосточный федеральный университет" (ДВФУ) | Carbosilan-siloxane dendrymers of the first generation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378790A (en) * | 1992-09-16 | 1995-01-03 | E. I. Du Pont De Nemours & Co. | Single component inorganic/organic network materials and precursors thereof |
| DE19517838A1 (en) * | 1995-05-16 | 1996-11-21 | Bayer Ag | Carbosilane dendrimers, a process for their preparation and their use |
| DE19603242A1 (en) * | 1995-05-16 | 1996-11-21 | Bayer Ag | Functional carbosilane dendrimers, organic-inorganic carbosilane hybrid materials, in each case a process for their preparation, a process for the preparation of paints from the functional carbosilane dendrimers and their use |
| US5677410A (en) * | 1995-05-16 | 1997-10-14 | Bayer Ag | Carbosilane-dendrimers, carbosilane-hybrid materials, methods for manufacturing them and a method for manufacturing coatings from the carbosilane-dendrimers |
| US5739218A (en) * | 1997-06-02 | 1998-04-14 | Dow Corning Corporation | Radially layered copoly (amidoamine-organosilicon) dendrimers |
-
1997
- 1997-03-20 DE DE19711650A patent/DE19711650C1/en not_active Expired - Fee Related
-
1998
- 1998-03-09 EP EP98104137A patent/EP0866086B1/en not_active Expired - Lifetime
- 1998-03-09 DE DE59809042T patent/DE59809042D1/en not_active Expired - Lifetime
- 1998-03-11 TW TW087103523A patent/TW446724B/en not_active IP Right Cessation
- 1998-03-12 US US09/041,378 patent/US5880305A/en not_active Expired - Lifetime
- 1998-03-13 JP JP10080584A patent/JPH10265483A/en active Pending
- 1998-03-19 KR KR10-1998-0009454A patent/KR100492216B1/en not_active IP Right Cessation
- 1998-03-19 RU RU98105516/04A patent/RU2193576C2/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE59809042D1 (en) | 2003-08-28 |
| US5880305A (en) | 1999-03-09 |
| EP0866086A2 (en) | 1998-09-23 |
| TW446724B (en) | 2001-07-21 |
| DE19711650C1 (en) | 1998-06-10 |
| JPH10265483A (en) | 1998-10-06 |
| KR19980080458A (en) | 1998-11-25 |
| EP0866086B1 (en) | 2003-07-23 |
| RU2193576C2 (en) | 2002-11-27 |
| EP0866086A3 (en) | 1999-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100492216B1 (en) | Process for The Preparation of SiOH-Functional Carbosilane Dendrimers | |
| US5663395A (en) | Process for the selective synthesis of silylalkyldisulphides | |
| JP2008537966A (en) | Process for producing monodisperse and narrowly dispersed monofunctional silicones | |
| CN107365416A (en) | A kind of method for preparing modified side chain polysiloxanes | |
| EP1068213B1 (en) | Novel aminoorganofunctionalsiloxanes | |
| TWI433871B (en) | Process for assembly of poss monomers | |
| JPH10237177A (en) | Production of network polysilane | |
| JP4271291B2 (en) | Polyethylene wax | |
| JPH0625420A (en) | Sulfonated silicone | |
| JPH0517487A (en) | New silane compound and its production | |
| Koželj et al. | Synthesis of polyhedral phenylsilsesquioxanes with KF as the source of the fluoride ion | |
| KR100899055B1 (en) | Grignard preparation of unsaturated organic compounds | |
| JPS6155516B2 (en) | ||
| JP3419173B2 (en) | New silane compounds suitable for coating inorganic powders | |
| JP2541060B2 (en) | Method for producing organosilicon compound | |
| JP3419153B2 (en) | Method for producing 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane | |
| JP2585099B2 (en) | Method for producing α, ω-dihydrogen organopolysiloxane | |
| JPH02117682A (en) | Production of 1,3-bis(hydroxyphenyl)disiloxane derivative | |
| EP1797103B1 (en) | Preparation of an aminoaryl-containing organosilicon compound and intermediate used in its preparation | |
| JP4276805B2 (en) | Novel silazane compound and method for producing the same, and novel silazane compound polymer and method for producing the same | |
| KR19990015037A (en) | Chlorohydrosilane derivatives and preparation method thereof | |
| CN111606950A (en) | Method for synthesizing silicon-based phosphorus cluster compound and product thereof | |
| KR100361367B1 (en) | Process for preparing an oxime type crosslinking agent used for silicone sealants | |
| RU2088603C1 (en) | Method of organosilicon resin producing | |
| JP3564530B2 (en) | Method for producing tetrakis (diarylsilyl) benzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20120503 Year of fee payment: 8 |
|
| LAPS | Lapse due to unpaid annual fee |